US20110017283A1 - Method and apparatus for deposition of a layer of an indium chalcogenide onto a substrate - Google Patents
Method and apparatus for deposition of a layer of an indium chalcogenide onto a substrate Download PDFInfo
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- US20110017283A1 US20110017283A1 US12/843,431 US84343110A US2011017283A1 US 20110017283 A1 US20110017283 A1 US 20110017283A1 US 84343110 A US84343110 A US 84343110A US 2011017283 A1 US2011017283 A1 US 2011017283A1
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- Prior art keywords
- indium
- chalcogen
- source
- reaction zone
- substrate
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- 229910052738 indium Inorganic materials 0.000 title claims abstract description 121
- 239000000758 substrate Substances 0.000 title claims abstract description 86
- -1 indium chalcogenide Chemical class 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title claims abstract description 59
- 230000008021 deposition Effects 0.000 title description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 72
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 63
- 229910052798 chalcogen Inorganic materials 0.000 claims abstract description 54
- 150000001787 chalcogens Chemical class 0.000 claims abstract description 54
- 238000010438 heat treatment Methods 0.000 claims abstract description 23
- 239000007789 gas Substances 0.000 claims description 76
- 239000002243 precursor Substances 0.000 claims description 41
- SIXIBASSFIFHDK-UHFFFAOYSA-N indium(3+);trisulfide Chemical compound [S-2].[S-2].[S-2].[In+3].[In+3] SIXIBASSFIFHDK-UHFFFAOYSA-N 0.000 claims description 32
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 31
- 239000008246 gaseous mixture Substances 0.000 claims description 30
- 239000012159 carrier gas Substances 0.000 claims description 24
- 238000000151 deposition Methods 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 17
- IBEFSUTVZWZJEL-UHFFFAOYSA-N trimethylindium Chemical compound C[In](C)C IBEFSUTVZWZJEL-UHFFFAOYSA-N 0.000 claims description 16
- 238000009826 distribution Methods 0.000 claims description 15
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- 239000005864 Sulphur Substances 0.000 claims description 14
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 13
- 239000006096 absorbing agent Substances 0.000 claims description 13
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 11
- 229910003437 indium oxide Inorganic materials 0.000 claims description 11
- 238000005229 chemical vapour deposition Methods 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 230000000087 stabilizing effect Effects 0.000 claims description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 5
- 150000002472 indium compounds Chemical class 0.000 claims description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims description 5
- 239000011733 molybdenum Substances 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052711 selenium Inorganic materials 0.000 claims description 4
- 150000001786 chalcogen compounds Chemical class 0.000 claims description 3
- 229910052733 gallium Inorganic materials 0.000 claims description 3
- 150000002898 organic sulfur compounds Chemical class 0.000 claims description 3
- 239000004065 semiconductor Substances 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical group CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims 1
- 125000000217 alkyl group Chemical group 0.000 claims 1
- 238000007599 discharging Methods 0.000 claims 1
- 125000000524 functional group Chemical group 0.000 claims 1
- 125000005843 halogen group Chemical group 0.000 claims 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 24
- 229910052786 argon Inorganic materials 0.000 description 12
- KTSFMFGEAAANTF-UHFFFAOYSA-N [Cu].[Se].[Se].[In] Chemical compound [Cu].[Se].[Se].[In] KTSFMFGEAAANTF-UHFFFAOYSA-N 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000010409 thin film Substances 0.000 description 7
- 239000011521 glass Substances 0.000 description 6
- VYMPLPIFKRHAAC-UHFFFAOYSA-N 1,2-ethanedithiol Chemical compound SCCS VYMPLPIFKRHAAC-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 239000011669 selenium Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- CJOBVZJTOIVNNF-UHFFFAOYSA-N cadmium sulfide Chemical compound [Cd]=S CJOBVZJTOIVNNF-UHFFFAOYSA-N 0.000 description 3
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 3
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 2
- 238000000231 atomic layer deposition Methods 0.000 description 2
- 150000004770 chalcogenides Chemical class 0.000 description 2
- 238000000224 chemical solution deposition Methods 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- AKUCEXGLFUSJCD-UHFFFAOYSA-N indium(3+);selenium(2-) Chemical compound [Se-2].[Se-2].[Se-2].[In+3].[In+3] AKUCEXGLFUSJCD-UHFFFAOYSA-N 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000002488 metal-organic chemical vapour deposition Methods 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- BLBQQEGAFVLNJA-UHFFFAOYSA-N argon sulfane Chemical compound S.[Ar] BLBQQEGAFVLNJA-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- HVMJUDPAXRRVQO-UHFFFAOYSA-N copper indium Chemical compound [Cu].[In] HVMJUDPAXRRVQO-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000001151 other effect Effects 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- VIDTVPHHDGRGAF-UHFFFAOYSA-N selenium sulfide Chemical compound [Se]=S VIDTVPHHDGRGAF-UHFFFAOYSA-N 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
- H01L31/0322—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising only AIBIIICVI chalcopyrite compounds, e.g. Cu In Se2, Cu Ga Se2, Cu In Ga Se2
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/305—Sulfides, selenides, or tellurides
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45595—Atmospheric CVD gas inlets with no enclosed reaction chamber
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/54—Apparatus specially adapted for continuous coating
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/06—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier
- H01L31/072—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier the potential barriers being only of the PN heterojunction type
- H01L31/0749—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier the potential barriers being only of the PN heterojunction type including a AIBIIICVI compound, e.g. CdS/CulnSe2 [CIS] heterojunction solar cells
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/184—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof the active layers comprising only AIIIBV compounds, e.g. GaAs, InP
- H01L31/1852—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof the active layers comprising only AIIIBV compounds, e.g. GaAs, InP comprising a growth substrate not being an AIIIBV compound
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/541—CuInSe2 material PV cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/544—Solar cells from Group III-V materials
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the present invention relates to a method for depositing a layer of an indium chalcogenide onto a substrate and an apparatus for performing the method.
- indium chalcogenide layers may be used in several applications, particularly in the field of semiconductor technology.
- indium chalcogenides are indium compounds containing a chalcogen, i.e. elements of group 16 of the periodic table of elements like oxygen, sulphur, selenium etc.
- a chalcogen i.e. elements of group 16 of the periodic table of elements like oxygen, sulphur, selenium etc.
- indium sulphide, indium selenide or indium oxide and mixtures thereof are such indium chalcogenides.
- the term chalcogenide is also defined as including an oxide material which has been at least partly converted to hydroxide.
- indium chalcogenides have been investigated in recent years in connection with solar cells of the second generation, also referred to as compound thin film solar cells.
- solar cells usually contain a substrate for structurally supporting the solar cell, e.g. a glass substrate, a back contact forming metal layer arranged upon the glass substrate, an absorber layer formed on the metal layer for example by copper indium selenide (CIS), copper indium gallium selenide (CIGS) or copper indium gallium sulphur selenide (CIGSSe), and a buffer layer deposited onto the absorber layer for which cadmium sulphide is widely used. Further on, the buffer layer is covered by a transparent conducting material like zinc oxide. The different layers can be formed by evaporation under vacuum conditions. However, this technique is not well-suited for low cost production at an industrial scale.
- Indium chalcogenide layers may be applied by chemical bath deposition. This method, however, requires a quite long processing time and produces contaminated wastewater which requires costly special treatment. Indium chalcogenide deposition by atomic layer deposition (ALD) or ion layer gas reaction (ILGAR) also requires long processing times. Physical vapour deposition (PVD) and sputtering are performed under vacuum and are consequently quite elaborate and costly. This is also the case for metal organic chemical vapour deposition (MOCVD).
- ALD atomic layer deposition
- ILGAR ion layer gas reaction
- PVD Physical vapour deposition
- MOCVD metal organic chemical vapour deposition
- the method according to the invention is based on the concept of providing an indium source in a reaction zone, providing a gaseous source of a chalcogen in the reaction zone, and heating the substrate.
- in the reaction zone at a pressure of approximately atmospheric ambient pressure indium originating from the indium source and chalcogen originating from the source of a chalcogen are converted to an indium chalcogenide being deposited onto a surface of a substrate.
- reaction zone refers to an area, in which conditions like temperature etc. are such that indium originating from an indium source located in the reaction zone and chalcogen originating from a source of chalcogen located in the reaction zone can be converted into indium chalcogenide and such that the indium chalcogenide can be deposited onto the surface of the substrate.
- the reaction zone will therefore be formed in the near neighborhood of the substrate and may include the surface of the substrate itself.
- substrate refers in principle to anything an indium chalcogenide layer can be deposited on. It might for example be a glass substrate with or without any layers deposited or formed before the deposition of the indium chalcogenide.
- approximately atmospheric ambient pressure means that the conversion of indium originating from the indium source and chalcogen originating from the source of a chalcogen to an indium chalcogenide takes place under a pressure having nearly the same pressure value as the atmospheric ambient pressure.
- the values might slightly differ due to gas flows within or out of the reactor or other effects. But in each case the reactor is not in any way evacuated and the pressure value at the substrate is not more than 50 mbar lower than the atmospheric ambient pressure. However, it might be more than 50 mbar higher.
- Heating might be performed in the reaction zone or before the substrates are fed into the reaction zone. In the latter case the substrates have to be heated such that their temperature at the time when they reach the reaction zone is still high enough to enable the described conversion in the reaction zone.
- the method according to the invention reduces complexity of indium chalcogenide deposition, as no vacuum is needed and as processing time is short as compared to chemical bath deposition. Furthermore, the method can be applied in inline production lines.
- a gaseous source of a chalcogen other sources such as a liquid or solid source of a chalcogen can be provided within the reaction zone such that the liquid or solid source of a chalcogen is converted directly into an indium chalcogenide without being previously transformed into a gaseous phase.
- a gaseous source of a chalcogen within the reaction zone this is, however, less advantageous.
- the indium chalcogenide to be deposited is selected from a group consisting of indium sulphide, indium selenide and indium oxide and the gaseous source of a chalcogen correspondingly provides a gaseous source of a chalcogen selected from a group consisting of sulphur, tellurium, selenium and oxygen.
- the gaseous source of a chalcogen correspondingly provides a gaseous source of sulphur.
- the gaseous source can be one or more compounds providing the respective chalcogen.
- the substrate is heated to a temperature between 130° C. and 380° C., preferably to a temperature between 230° C. and 330° C.
- the substrate is moved during the depositing of the indium chalcogenide, as it has turned out that in this way the homogeneity of the deposited indium chalcogenide layer can be improved.
- indium chalcogenide layers are deposited sequentially.
- the resulting several sub-layers form together the final layer having the desired thickness.
- properties of the deposited indium chalcogenide layer can be improved.
- it allows a high throughput in manufacturing of thin film solar cells, for example, particularly in connection with inline production lines.
- indium chalcogenide layers can be deposited at significant higher growth rates as it is possible using other techniques like vacuum MOCVD.
- the indium chalcogenide layer is deposited at a growth rate between 1 and 60 nm/s, especially preferred at a growth rate greater than 5 nm/s.
- the substrate is preheated before entering the reaction zone or even before entering an apparatus for carrying out the method according to the invention.
- the latter is especially advantageous for an inline production, for example.
- Preheating might be performed such that on entering the reaction zone the temperature of the substrates is still high enough to enable the described conversion of indium and a chalcogen into an indium chalcogenide, so that no further heating of the substrates needs to be done.
- preheating might be performed such that an additional heating within the reaction zone is necessary. In an embodiment of the invention according to the latter case, such additional heating is performed in order to enable the desired conversion of indium originating from the indium source and the chalcogen originating from the source of a chalcogen to an indium chalcogenide.
- the indium source is provided in the reaction zone by depositing an indium containing compound, preferably indium oxide, onto the surface of the substrate and arranging the substrate at least partly in the reaction zone.
- the indium containing compound might be deposited onto the substrate by sputtering or chemical vapor deposition.
- the indium containing compound might be itself an indium chalcogenide which has been previously deposited onto the substrate by the method according to the invention.
- indium oxide as an indium source
- another indium chalcogenide other than indium oxide will be formed by applying the method according to the invention.
- a gaseous source of sulphur preferably hydrogen sulphide
- indium originating for the indium oxide and sulphur originating from the gaseous source of sulphur would be converted into indium sulphide being deposited onto the surface of the substrate.
- a gaseous mixture containing a carrier gas, the indium source and the chalcogen source is provided in the reaction zone.
- a carrier gas Preferably an inert gas is used as carrier gas; especially preferred is the usage of nitrogen or argon gas.
- the gaseous mixture is preferably delivered to the substrate to be coated in a laminar flow. In this way the homogeneity of the deposited indium chalcogenide layers can be improved.
- the gaseous mixture is advantageously kept at a temperature chosen such that gas phase reaction of the gaseous mixture is sufficiently controlled. Therefore the gaseous mixture is kept at a temperature such that in the gaseous mixture the conversion of indium and of a chalcogen into an indium chalcogenide does not, or at least only to a non-relevant extent, take place until the gaseous mixture reaches the reaction zone.
- the gaseous mixture is kept at a temperature between 30° C. and 240° C., preferably at a temperature between 40° C. and 210° C., and even more preferably at a temperature between 50° C. and 200° C., until it reaches the reaction zone.
- an indium containing a precursor gas is premixed with a chalcogen containing a precursor gas and a carrier gas and the resulting mixture is delivered as gaseous mixture into the reaction zone.
- a gaseous component already contained in the indium and/or the chalcogen containing precursor gas is used as a carrier gas, so that no further carrier gas has to be added in order to obtain the desired gaseous mixture.
- an inert gas like nitrogen or argon contained in one of the precursor gases can be used as carrier gas.
- a stabilizing adduct group is an adduct group that stabilizes the gaseous mixture such that the conversion of the precursor gases into indium chalcogenide is suppressed until the gaseous mixture reaches the reaction zone.
- the stabilizing adduct group is preferably based on an element selected from the group consisting of sulphur, oxygen and electron donating nitrogen. Electron donating nitrogen based adduct groups are e.g. amine containing compounds.
- chelating agents can be used as stabilizing adduct groups of the indium containing precursor gas, for example tetramethylethylendiamine. Another example is the usage of 1,2-etanedithiol in or as a chalcogen containing precursor gas, as it simultaneously stabilizes certain indium containing precursor gases like precursor gases containing trimethylindium.
- premixing precursor gases it is also possible to form the gaseous mixture by mixing an indium containing precursor gas with a chalcogen containing precursor gas and a carrier gas close to or in the reaction zone.
- a gaseous component contained in the indium and/or the chalcogen containing a precursor gas is preferably used as carrier gas.
- At least one precursor gas is provided via at least one distribution head.
- distribution heads allow a controlled gas flow and are per se known from methods and apparatus of chemical vapour deposition.
- temperature controlled distribution heads are used, which make it possible to improve uniformity of the deposited layer.
- the substrate is advantageously moved during the deposition of the indium chalcogenide.
- the substrate is moved relatively to the at least one distribution head or vice versa.
- an at atmospheric ambient pressure volatile chalcogen compound preferably a sulphur compound and especially preferably a hydrogen sulphide or an organosulphur compound
- the gaseous chalcogen source is used as the gaseous chalcogen source.
- Organosulphur compounds are for example alkyl sulphides.
- an ethanethiol, particularly 1,2-ethanedithiol may be used as a sulphur source.
- sulphur sources being solid at room temperature might be advantageous against the background of maintenance and handling aspects.
- different gaseous chalcogen sources can be mixed.
- the indium chalcogenide layer preferably an indium sulphide layer, is deposited as a buffer layer of a solar cell.
- a metal layer preferably a molybdenum layer
- an absorber layer preferably an absorber layer containing a compound represented by the formula Cu(In,Ga)(S,Se) 2 —or more precisely Cu(In 1-a Ga a )(S b ,Se 1-b ) 2 , where 0 ⁇ a,b ⁇ 1—, are deposited onto the substrate before the indium chalcogenide is deposited onto the surface of the substrate.
- This allows a fabrication of CIS or CIGS solar cells at industrial scale and favorable cost.
- the deposition of indium sulphide as indium chalcogenide is especially preferred.
- the solar cell according to the invention is based on the concept of forming a buffer layer by chemical vapor deposition of an indium chalcogenide at approximately atmospheric ambient pressure. In this way thin film solar cells of reduced complexity can be provided.
- indium sulphide is used as indium chalcogenide.
- the apparatus according to the invention contains a reactor, into which substrates can be introduced, a gas inlet slot for feeding gases into the reactor, a transport device for moving the substrates through the reactor, and at least one premixing device for premixing an indium containing a precursor gas with a chalcogen containing the precursor gas.
- a gaseous mixture produced in the premixing device can be fed from the premixing device into the reactor via the gas inlet slot.
- the transport device can be realized by known transport systems, e.g. push or pull rod systems or a conveyor belt.
- gas inlet slots are provided, which are arranged in a distance from each other in a transport direction of the transport device.
- the gas inlet slots are arranged such that with each gas inlet slot a further sublayer can be deposited. In this way several sublayers can comfortably be deposited on a substrate passing the several gas inlet slots.
- Each gas inlet slot might be connected to the same premixing device or to a separate premixing device.
- a laminar flow of the gaseous mixture from the gas inlet slots to the substrates can be realized.
- the apparatus contains at least one temperature control device for controlling the temperature of the gaseous mixture in at least one premixing device or at least one gas inlet slot.
- the at least one control unit might be realized as an open-loop control device or as a closed-loop device, the latter one being connected to heating or cooling devices for the gaseous mixture or materials fed into the at least one premixing device.
- At least one coater head is provided as a gas inlet slot.
- coater heads are known from chemical vapor deposition apparatus.
- the at least one coater head is a temperature controlled coater head.
- the apparatus contains a heating device for heating the substrates.
- substrates can be preheated outside of the apparatus and additionally heated within the apparatus to a temperature required in the reaction zone. Also it is possible to heat the substrates to the required temperature within the apparatus without any previous heating of the substrates. If instead the apparatus does not contain any heating device, the substrates have to be heated before entering the apparatus in such that their temperature on entering the reaction zone is still high enough to enable the conversion of indium originating from the indium source and the chalcogen originating from the source of a chalcogen to an indium chalcogenide.
- FIG. 1 is an illustration of a first embodiment of the method according to the invention
- FIG. 2 is an illustration of a second embodiment of the method according to the invention.
- FIG. 3 is an illustration of a first embodiment of an apparatus according to the invention simultaneously illustrating a third embodiment of the method according to the invention
- FIG. 4 is an illustration of a second embodiment of the apparatus according to the invention in a schematic drawing and a fourth embodiment of the method according to the invention
- FIG. 5 is an illustration of a thin film solar cell according to the invention.
- FIG. 1 there is shown schematically a sequence of method steps performed in a reactor 70 and in this way illustrates a first embodiment of the method according to the invention.
- Substrates 1 onto a surface 2 of which an indium oxide 3 layer has been deposited, are introduced into the reactor 70 .
- the reactor 70 has a heating device 72 for heating the substrates 1 .
- an external heating device is used. It is however obvious to a person skilled in the art that also internal heating devices arranged in a chamber 71 of the reactor 70 can be used.
- the substrates 1 are heated by the heating device 72 .
- open ends of the reactor 70 can be provided, so that the substrates 1 can easily be transported into and through the reactor 72 as indicated by a direction of a substrate transport 5 .
- gas locks particularly gas curtains, can be provided in order to prevent intrusion of contaminations into the reactor 70 . Examples of such gas locks 73 a , 73 b are schematically indicated in FIG. 4 .
- the substrate transport is realized by a per se known transport device, e.g. a pull or push rod system or a conveyer-belt, which is not depicted in the figures for the purpose of enhanced clarity.
- the transport device the substrates 1 can be transported through the reactor 70 .
- the substrate 1 carrying the indium oxide layer 3 is transported from the left to the right side by the transport device.
- the substrate 1 reaches a reaction zone 8 and is arranged in it for a certain time.
- the indium oxide 3 deposited onto the substrate 1 is arranged in the reaction zone 8 and serves as an indium source.
- a gaseous source of a chalcogen in the embodiment depicted in FIG. 1 represented by a mixture 9 of hydrogen sulphide and argon gas used as a carrier gas, is fed into the reaction zone 8 via a gas inlet 74 .
- a gaseous source of a chalcogen in the embodiment depicted in FIG. 1 represented by a mixture 9 of hydrogen sulphide and argon gas used as a carrier gas, is fed into the reaction zone 8 via a gas inlet 74 .
- FIG. 2 schematically illustrates a further embodiment of the method according to the invention.
- the substrates 1 without any indium source deposited thereon are introduced into the reactor 70 .
- These substrates 1 are again transported by a not depicted transport device in the direction of transport 5 into a first reaction zone 18 a .
- a gas inlet 75 a trimethylindium and nitrogen 77 a are fed as an indium containing precursor gas and as a carrier gas into the first reaction zone 18 a .
- a gas inlet 75 b also a mixture 79 a of hydrogen sulphide and argon gas as a carrier gas is fed into the first reaction zone 18 a .
- the mixture 79 a of hydrogen sulphide and argon represents a chalcogen containing a precursor gas.
- the indium containing precursor gas formed by the mixture 77 a of trimethylindium and nitrogen gas is mixed with the mixture 79 a of hydrogen sulphide and argon, so that a gaseous mixture containing the carrier gases nitrogen and argon, trimethylindium as an indium source and hydrogen sulphide as chalcogen source is provided in the first reaction zone 18 a .
- indium originating from the mixture 77 a of trimethylindium and nitrogen and sulphur originating from the mixture 79 b of hydrogen sulphide and argon carrier gas are converted into indium sulphide and deposited onto the surface 2 of the substrate 1 as indium sulphide sublayer.
- the substrate 1 carrying the indium sulphide sub-layer 18 a is transported into a second reaction zone 18 b . All transport of the substrates 1 is preferably done continuously. This means that the substrates 1 are continuously moved relatively to the reactor 70 .
- indium sulphide sublayers make it possible to produce indium sulphide layers of enhanced homogeneity. Furthermore, a thickness of the indium sulphide layer can be quite easily controlled. In principle, any number of indium sulphide sublayers can be deposited by elongating the reactor 70 and providing additional gas inlets.
- FIG. 3 schematically illustrates a further embodiment of the method according to the invention and simultaneously a first embodiment of an apparatus according to the invention.
- the apparatus schematically depicted in FIG. 3 differs from the one of FIG. 2 in such that two premixing devices 81 a , 81 b are provided.
- a mixture 83 of trimethylindium and nitrogen forming together an indium containing precursor gas and a mixture 85 of 1,2-ethanedithiol and nitrogen are fed into each of the premixing devices 81 a , 81 b .
- the mixture 85 of 1,2-ethanedithiol and nitrogen represents a chalcogen containing precursor gas.
- the materials are premixed in the premixing devices 81 a , 81 b .
- the resulting gaseous mixtures 86 are fed into the reactor 70 via inlet slots 87 a and 87 b .
- the gaseous mixtures are fed into the first 18 a and second reaction zone 18 b , respectively.
- indium and sulphide contained in the gaseous mixture are converted to indium sulphide.
- in the first reaction zone 18 a an indium sulphide sublayer 27 a is deposited onto the surface 2 of the substrate 1
- a further indium sulphide sublayer 27 b is deposited onto the previously deposited indium sulphide sublayer 27 a.
- trimethylindium is solid at room temperature.
- a trimethylindium source is therefore preferably heated to a temperature between 25° C. and 75° C., so that the material partly sublimes.
- nitrogen is preferably provided as the carrier gas for trimethylindium vapor. Flowing above the trimethylindium source it carries away trimethylindium vapor and delivers it into the premixing devices. In this way growth rates of the indium sulphide layer can be improved.
- 1,2-ethanedithiol is premixed with trimethylindium.
- these materials can also be used in the embodiments of FIGS. 1 and 2 and vice versa.
- other material combinations are possible.
- trimethylindium with a nitrogen carrier gas as indium containing a precursor gas in combination with hydrogen sulphide diluted into argon has proven itself.
- hydrogen sulphide diluted into argon represents the chalcogen containing a precursor gas.
- Such a gaseous mixture is preferably kept at a temperature of about 50° C. until it is fed into the reaction zone.
- FIG. 4 shows in a schematic illustration a further embodiment of the apparatus according to the invention and illustrates simultaneously a further embodiment of the method according to the invention.
- the apparatus differs from the one known from FIG. 3 such that only one premixing device 82 is provided instead of two.
- the gas inlets are realized by temperature controlled distribution heads 91 a , 91 b .
- the gaseous mixture 86 is consequently fed from the premixing device 82 into the reactor 70 and in the first and second reaction zones 18 a , 18 b via openings 89 a , 89 b of the temperature controlled distribution heads 91 a , 91 b .
- the precursor gases being part of the gaseous mixture 86 are provided via the distribution heads 91 a , 91 b.
- premixing device 82 By providing one premixing device 82 for several, in this embodiment two, distribution heads 91 a , 91 b or gas inlets in general, complexity of the apparatus can be reduced. Moreover, the number of premixing devices and the number of gas inlets or distribution heads each premixing device supplies with the gaseous mixture can be adapted to individual needs.
- Distribution heads and particularly temperature controlled distribution heads, can obviously also be provided instead of gas inlets in the embodiments of FIGS. 1 to 3 .
- Temperature controlled distribution heads are, however, particularly advantageous in the embodiments of FIGS. 3 and 4 as they facilitate the temperature control of the gaseous mixture 86 .
- FIGS. 1 to 4 All the apparatus depicted in FIGS. 1 to 4 can easily be integrated in inline production lines, so that a cost efficient deposition of indium chalcogenide layers at an industrial scale becomes possible.
- thin film solar cells can be advantageously produced using one of the methods and one of the apparatus according to the depicted embodiments.
- the heating device 72 can be omitted, if the substrates 1 are preheated outside the reactor 70 such that on reaching the reaction zone 8 ; 18 a , 18 b their temperature is still high enough to enable the conversion of indium originating from the indium source and the chalcogen originating from the source of a chalcogen to an indium chalcogenide.
- FIG. 5 schematically illustrates a solar cell 49 according to the invention. It contains a glass substrate 50 covered by a molybdenum layer 52 .
- a CIGS layer 54 serving as absorber layer is formed on the molybdenum layer.
- an indium sulphide layer 57 formed by chemical vapor deposition at approximately atmospheric ambient pressure is provided as a buffer layer.
- a zinc oxide layer 59 is provided on the indium sulphide layer 57 as a transparent conducting layer.
- the solar cell 49 can be manufactured using one of the methods and apparatus illustrated in FIGS. 1 to 4 .
- the substrate 1 in FIGS. 1 to 4 would then be formed by the glass substrate 50 , the molybdenum layer 52 and the CIGS layer 54 .
- the surface 2 onto which the indium sulphide is deposited, would then be an upper surface of the CIGS layer 54 .
- the term substrate refers to anything an indium chalcogenide layer can be deposited on. In particular it can mean a glass substrate carrying a metal back contact layer and an absorber layer of a thin film solar cell.
Abstract
A method deposits a layer of an indium chalcogenide onto a substrate. The method includes the steps of: providing an indium source in a reaction zone, providing a gaseous source of a chalcogen in the reaction zone, and heating the substrate. Thereby in the reaction zone, at a pressure of approximately atmospheric ambient pressure, the indium originating from the indium source and the chalcogen originating from the source of a chalcogen are converted to an indium chalcogenide being deposited onto the surface of the substrate.
Description
- This application claims the priority, under 35 U.S.C. §119, of European application EP 09 009 994.6, filed Jul. 24, 2009; the prior application is here-with incorporated by reference in its entirety.
- The present invention relates to a method for depositing a layer of an indium chalcogenide onto a substrate and an apparatus for performing the method.
- Indium chalcogenide layers, sometimes also referred to as indium chalcogenide films, may be used in several applications, particularly in the field of semiconductor technology. For the purpose of the present invention indium chalcogenides are indium compounds containing a chalcogen, i.e. elements of group 16 of the periodic table of elements like oxygen, sulphur, selenium etc. For example, indium sulphide, indium selenide or indium oxide and mixtures thereof are such indium chalcogenides. For the purposes of the present invention, the term chalcogenide is also defined as including an oxide material which has been at least partly converted to hydroxide.
- In particular, indium chalcogenides have been investigated in recent years in connection with solar cells of the second generation, also referred to as compound thin film solar cells. Such solar cells usually contain a substrate for structurally supporting the solar cell, e.g. a glass substrate, a back contact forming metal layer arranged upon the glass substrate, an absorber layer formed on the metal layer for example by copper indium selenide (CIS), copper indium gallium selenide (CIGS) or copper indium gallium sulphur selenide (CIGSSe), and a buffer layer deposited onto the absorber layer for which cadmium sulphide is widely used. Further on, the buffer layer is covered by a transparent conducting material like zinc oxide. The different layers can be formed by evaporation under vacuum conditions. However, this technique is not well-suited for low cost production at an industrial scale.
- This problem has been partly addressed by the invention described in international patent disclosure WO 2009/033674. It provides for a thermal conversion of metallic precursor layers into a semiconducting absorber layer like CIGS at approximately atmospheric pressure. In this way absorber layers can be produced in an industrial scale at low complexity. It even allows an inline production of absorber layers.
- However, thin film solar cells also require a buffer layer. As the deposition of cadmium sulphide as a buffer layer is problematic with respect to environmental risks and the prohibition of the usage of cadmium in certain countries, alternative materials have been investigated. Indium chalcogenides like indium sulphide have proven as promising alternatives to cadmium sulphide.
- Indium chalcogenide layers may be applied by chemical bath deposition. This method, however, requires a quite long processing time and produces contaminated wastewater which requires costly special treatment. Indium chalcogenide deposition by atomic layer deposition (ALD) or ion layer gas reaction (ILGAR) also requires long processing times. Physical vapour deposition (PVD) and sputtering are performed under vacuum and are consequently quite elaborate and costly. This is also the case for metal organic chemical vapour deposition (MOCVD).
- It is accordingly an object of the invention to provide a method and an apparatus for deposition of a layer of an indium chalcogenide onto a substrate which overcome the above-mentioned disadvantages of the prior art methods and devices of this general type, which provides a low-complexity method to deposit an indium chalcogenide layer onto a substrate. Moreover, it is a further object of the invention to provide a solar cell that can be produced at an industrial scale at favourable cost.
- The method according to the invention is based on the concept of providing an indium source in a reaction zone, providing a gaseous source of a chalcogen in the reaction zone, and heating the substrate. Thereby in the reaction zone, at a pressure of approximately atmospheric ambient pressure indium originating from the indium source and chalcogen originating from the source of a chalcogen are converted to an indium chalcogenide being deposited onto a surface of a substrate.
- For the purpose of the present invention, reaction zone refers to an area, in which conditions like temperature etc. are such that indium originating from an indium source located in the reaction zone and chalcogen originating from a source of chalcogen located in the reaction zone can be converted into indium chalcogenide and such that the indium chalcogenide can be deposited onto the surface of the substrate. In most cases the reaction zone will therefore be formed in the near neighborhood of the substrate and may include the surface of the substrate itself. Furthermore, substrate refers in principle to anything an indium chalcogenide layer can be deposited on. It might for example be a glass substrate with or without any layers deposited or formed before the deposition of the indium chalcogenide.
- For the purpose of the present invention approximately atmospheric ambient pressure means that the conversion of indium originating from the indium source and chalcogen originating from the source of a chalcogen to an indium chalcogenide takes place under a pressure having nearly the same pressure value as the atmospheric ambient pressure. The values might slightly differ due to gas flows within or out of the reactor or other effects. But in each case the reactor is not in any way evacuated and the pressure value at the substrate is not more than 50 mbar lower than the atmospheric ambient pressure. However, it might be more than 50 mbar higher.
- Heating might be performed in the reaction zone or before the substrates are fed into the reaction zone. In the latter case the substrates have to be heated such that their temperature at the time when they reach the reaction zone is still high enough to enable the described conversion in the reaction zone.
- The method according to the invention reduces complexity of indium chalcogenide deposition, as no vacuum is needed and as processing time is short as compared to chemical bath deposition. Furthermore, the method can be applied in inline production lines.
- It shall be mentioned that instead of a gaseous source of a chalcogen other sources such as a liquid or solid source of a chalcogen can be provided within the reaction zone such that the liquid or solid source of a chalcogen is converted directly into an indium chalcogenide without being previously transformed into a gaseous phase. Compared to providing, in accordance with the method according to the invention, a gaseous source of a chalcogen within the reaction zone, this is, however, less advantageous.
- In a preferred embodiment of the method according to the invention the indium chalcogenide to be deposited is selected from a group consisting of indium sulphide, indium selenide and indium oxide and the gaseous source of a chalcogen correspondingly provides a gaseous source of a chalcogen selected from a group consisting of sulphur, tellurium, selenium and oxygen. These materials have proven themselves. In an especially preferred embodiment, indium sulphide is deposited and the gaseous source of a chalcogen correspondingly provides a gaseous source of sulphur. In each embodiment the gaseous source can be one or more compounds providing the respective chalcogen.
- In an advantageous embodiment the substrate is heated to a temperature between 130° C. and 380° C., preferably to a temperature between 230° C. and 330° C.
- Preferably, the substrate is moved during the depositing of the indium chalcogenide, as it has turned out that in this way the homogeneity of the deposited indium chalcogenide layer can be improved.
- In an advantageous embodiment several indium chalcogenide layers are deposited sequentially. The resulting several sub-layers form together the final layer having the desired thickness. In doing so, properties of the deposited indium chalcogenide layer can be improved. Furthermore, it allows a high throughput in manufacturing of thin film solar cells, for example, particularly in connection with inline production lines.
- Using the method according to the invention indium chalcogenide layers can be deposited at significant higher growth rates as it is possible using other techniques like vacuum MOCVD. In a preferred embodiment therefore the indium chalcogenide layer is deposited at a growth rate between 1 and 60 nm/s, especially preferred at a growth rate greater than 5 nm/s.
- In a preferred embodiment of the invention the substrate is preheated before entering the reaction zone or even before entering an apparatus for carrying out the method according to the invention. The latter is especially advantageous for an inline production, for example. Preheating might be performed such that on entering the reaction zone the temperature of the substrates is still high enough to enable the described conversion of indium and a chalcogen into an indium chalcogenide, so that no further heating of the substrates needs to be done. Or preheating might be performed such that an additional heating within the reaction zone is necessary. In an embodiment of the invention according to the latter case, such additional heating is performed in order to enable the desired conversion of indium originating from the indium source and the chalcogen originating from the source of a chalcogen to an indium chalcogenide.
- In one embodiment of the method according to the invention the indium source is provided in the reaction zone by depositing an indium containing compound, preferably indium oxide, onto the surface of the substrate and arranging the substrate at least partly in the reaction zone. The indium containing compound might be deposited onto the substrate by sputtering or chemical vapor deposition. In particular, the indium containing compound might be itself an indium chalcogenide which has been previously deposited onto the substrate by the method according to the invention. In case of using indium oxide as an indium source, another indium chalcogenide other than indium oxide will be formed by applying the method according to the invention. For example, a gaseous source of sulphur, preferably hydrogen sulphide, might be fed into the reaction zone and in this way be provided therein. In this case indium originating for the indium oxide and sulphur originating from the gaseous source of sulphur would be converted into indium sulphide being deposited onto the surface of the substrate.
- In an alternative embodiment of the method according to the invention a gaseous mixture containing a carrier gas, the indium source and the chalcogen source is provided in the reaction zone. Preferably an inert gas is used as carrier gas; especially preferred is the usage of nitrogen or argon gas.
- The gaseous mixture is preferably delivered to the substrate to be coated in a laminar flow. In this way the homogeneity of the deposited indium chalcogenide layers can be improved.
- Until reaching the reaction zone, the gaseous mixture is advantageously kept at a temperature chosen such that gas phase reaction of the gaseous mixture is sufficiently controlled. Therefore the gaseous mixture is kept at a temperature such that in the gaseous mixture the conversion of indium and of a chalcogen into an indium chalcogenide does not, or at least only to a non-relevant extent, take place until the gaseous mixture reaches the reaction zone. Advantageously, the gaseous mixture is kept at a temperature between 30° C. and 240° C., preferably at a temperature between 40° C. and 210° C., and even more preferably at a temperature between 50° C. and 200° C., until it reaches the reaction zone.
- In a preferred embodiment an indium containing a precursor gas is premixed with a chalcogen containing a precursor gas and a carrier gas and the resulting mixture is delivered as gaseous mixture into the reaction zone. Advantageously, a gaseous component already contained in the indium and/or the chalcogen containing precursor gas is used as a carrier gas, so that no further carrier gas has to be added in order to obtain the desired gaseous mixture. For example an inert gas like nitrogen or argon contained in one of the precursor gases can be used as carrier gas.
- Advantageously, at least one of the precursor gases contains a stabilizing adduct group. For the purpose of the present invention, a stabilizing adduct group is an adduct group that stabilizes the gaseous mixture such that the conversion of the precursor gases into indium chalcogenide is suppressed until the gaseous mixture reaches the reaction zone. The stabilizing adduct group is preferably based on an element selected from the group consisting of sulphur, oxygen and electron donating nitrogen. Electron donating nitrogen based adduct groups are e.g. amine containing compounds. Moreover, chelating agents can be used as stabilizing adduct groups of the indium containing precursor gas, for example tetramethylethylendiamine. Another example is the usage of 1,2-etanedithiol in or as a chalcogen containing precursor gas, as it simultaneously stabilizes certain indium containing precursor gases like precursor gases containing trimethylindium.
- Instead of premixing precursor gases, it is also possible to form the gaseous mixture by mixing an indium containing precursor gas with a chalcogen containing precursor gas and a carrier gas close to or in the reaction zone. Again, a gaseous component contained in the indium and/or the chalcogen containing a precursor gas is preferably used as carrier gas.
- According to a preferred embodiment of the invention, in both cases, precursor gases premixed or not, at least one precursor gas is provided via at least one distribution head. Such distribution heads allow a controlled gas flow and are per se known from methods and apparatus of chemical vapour deposition. Preferably, temperature controlled distribution heads are used, which make it possible to improve uniformity of the deposited layer. As already discussed above, the substrate is advantageously moved during the deposition of the indium chalcogenide. Preferably, the substrate is moved relatively to the at least one distribution head or vice versa.
- In a preferred embodiment of the method according to the invention, an at atmospheric ambient pressure volatile chalcogen compound, preferably a sulphur compound and especially preferably a hydrogen sulphide or an organosulphur compound, is used as the gaseous chalcogen source. Organosulphur compounds are for example alkyl sulphides. Also an ethanethiol, particularly 1,2-ethanedithiol, may be used as a sulphur source. Particularly, sulphur sources being solid at room temperature might be advantageous against the background of maintenance and handling aspects. Obviously, different gaseous chalcogen sources can be mixed.
- In both cases, precursor gases premixed or not, the usage of an indium containing precursor gas containing trimethylindium and nitrogen carrier gas in combination with a chalcogenide containing a precursor gas containing hydrogen sulphide diluted into argon carrier gas has proven itself.
- In one embodiment of the method according to the invention the indium chalcogenide layer, preferably an indium sulphide layer, is deposited as a buffer layer of a solar cell.
- In a preferred embodiment a metal layer, preferably a molybdenum layer, and subsequently an absorber layer, preferably an absorber layer containing a compound represented by the formula Cu(In,Ga)(S,Se)2—or more precisely Cu(In1-aGaa)(Sb,Se1-b)2, where 0≦a,b≦1—, are deposited onto the substrate before the indium chalcogenide is deposited onto the surface of the substrate. This, for example, allows a fabrication of CIS or CIGS solar cells at industrial scale and favorable cost. In connection with this embodiment the deposition of indium sulphide as indium chalcogenide is especially preferred.
- The solar cell according to the invention is based on the concept of forming a buffer layer by chemical vapor deposition of an indium chalcogenide at approximately atmospheric ambient pressure. In this way thin film solar cells of reduced complexity can be provided.
- In a preferred embodiment of the solar cell according to the invention indium sulphide is used as indium chalcogenide.
- The apparatus according to the invention contains a reactor, into which substrates can be introduced, a gas inlet slot for feeding gases into the reactor, a transport device for moving the substrates through the reactor, and at least one premixing device for premixing an indium containing a precursor gas with a chalcogen containing the precursor gas. A gaseous mixture produced in the premixing device can be fed from the premixing device into the reactor via the gas inlet slot. The transport device can be realized by known transport systems, e.g. push or pull rod systems or a conveyor belt.
- In an advantageous embodiment of the apparatus several gas inlet slots are provided, which are arranged in a distance from each other in a transport direction of the transport device. Preferably, the gas inlet slots are arranged such that with each gas inlet slot a further sublayer can be deposited. In this way several sublayers can comfortably be deposited on a substrate passing the several gas inlet slots.
- Each gas inlet slot might be connected to the same premixing device or to a separate premixing device.
- Advantageously, a laminar flow of the gaseous mixture from the gas inlet slots to the substrates can be realized.
- In a preferred embodiment, the apparatus contains at least one temperature control device for controlling the temperature of the gaseous mixture in at least one premixing device or at least one gas inlet slot. The at least one control unit might be realized as an open-loop control device or as a closed-loop device, the latter one being connected to heating or cooling devices for the gaseous mixture or materials fed into the at least one premixing device.
- In a preferred embodiment at least one coater head is provided as a gas inlet slot. As mentioned above, such coater heads are known from chemical vapor deposition apparatus. Preferably, the at least one coater head is a temperature controlled coater head.
- In yet another preferred embodiment the apparatus contains a heating device for heating the substrates. In this way, substrates can be preheated outside of the apparatus and additionally heated within the apparatus to a temperature required in the reaction zone. Also it is possible to heat the substrates to the required temperature within the apparatus without any previous heating of the substrates. If instead the apparatus does not contain any heating device, the substrates have to be heated before entering the apparatus in such that their temperature on entering the reaction zone is still high enough to enable the conversion of indium originating from the indium source and the chalcogen originating from the source of a chalcogen to an indium chalcogenide.
- Other features which are considered as characteristic for the invention are set forth in the appended claims.
- Although the invention is illustrated and described herein as embodied in a method and an apparatus for deposition of a layer of an indium chalcogenide onto a substrate, it is nevertheless not intended to be limited to the details shown, since various modifications and structural changes may be made therein without departing from the spirit of the invention and within the scope and range of equivalents of the claims.
- The construction and method of operation of the invention, however, together with additional objects and advantages thereof will be best understood from the following description of specific embodiments when read in connection with the accompanying drawings.
- The invention will be explained in more detail below with reference to figures. Elements exercising essentially similar effects are, as far as this appears appropriate, marked with equal reference signs.
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FIG. 1 is an illustration of a first embodiment of the method according to the invention; -
FIG. 2 is an illustration of a second embodiment of the method according to the invention; -
FIG. 3 is an illustration of a first embodiment of an apparatus according to the invention simultaneously illustrating a third embodiment of the method according to the invention; -
FIG. 4 is an illustration of a second embodiment of the apparatus according to the invention in a schematic drawing and a fourth embodiment of the method according to the invention; -
FIG. 5 is an illustration of a thin film solar cell according to the invention. - Referring now to the figures of the drawing in detail and first, particularly, to
FIG. 1 thereof, there is shown schematically a sequence of method steps performed in areactor 70 and in this way illustrates a first embodiment of the method according to the invention.Substrates 1, onto asurface 2 of which anindium oxide 3 layer has been deposited, are introduced into thereactor 70. Thereactor 70 has aheating device 72 for heating thesubstrates 1. In the embodiment ofFIG. 1 an external heating device is used. It is however obvious to a person skilled in the art that also internal heating devices arranged in achamber 71 of thereactor 70 can be used. Thesubstrates 1 are heated by theheating device 72. Therefore, open ends of thereactor 70 can be provided, so that thesubstrates 1 can easily be transported into and through thereactor 72 as indicated by a direction of asubstrate transport 5. At the open ends of the reactors depicted inFIGS. 1 to 4 , gas locks, particularly gas curtains, can be provided in order to prevent intrusion of contaminations into thereactor 70. Examples ofsuch gas locks FIG. 4 . - In the embodiments illustrated in
FIGS. 1 to 4 , the substrate transport is realized by a per se known transport device, e.g. a pull or push rod system or a conveyer-belt, which is not depicted in the figures for the purpose of enhanced clarity. With the help of the transport device thesubstrates 1 can be transported through thereactor 70. In the case ofFIG. 1 , thesubstrate 1 carrying theindium oxide layer 3 is transported from the left to the right side by the transport device. In this way thesubstrate 1 reaches areaction zone 8 and is arranged in it for a certain time. During this time also theindium oxide 3 deposited onto thesubstrate 1 is arranged in thereaction zone 8 and serves as an indium source. Moreover, a gaseous source of a chalcogen, in the embodiment depicted inFIG. 1 represented by amixture 9 of hydrogen sulphide and argon gas used as a carrier gas, is fed into thereaction zone 8 via agas inlet 74. As a consequence of the heating of thesubstrate 1, in thereaction zone 8 indium originating from theindium oxide 3 and sulphur originating from the hydrogensulphide argon mixture 9 fed into the reaction zone are converted at approximately atmospheric ambient pressure into indium sulphide, so that as a result anindium sulphide 7 layer is comfortably deposited on thesurface 2 of thesubstrate 1. -
FIG. 2 schematically illustrates a further embodiment of the method according to the invention. According to this embodiment, thesubstrates 1 without any indium source deposited thereon are introduced into thereactor 70. Thesesubstrates 1 are again transported by a not depicted transport device in the direction oftransport 5 into afirst reaction zone 18 a. By agas inlet 75 a trimethylindium andnitrogen 77 a are fed as an indium containing precursor gas and as a carrier gas into thefirst reaction zone 18 a. By agas inlet 75 b also amixture 79 a of hydrogen sulphide and argon gas as a carrier gas is fed into thefirst reaction zone 18 a. In doing so, themixture 79 a of hydrogen sulphide and argon represents a chalcogen containing a precursor gas. In thefirst reaction zone 18 a, the indium containing precursor gas formed by themixture 77 a of trimethylindium and nitrogen gas is mixed with themixture 79 a of hydrogen sulphide and argon, so that a gaseous mixture containing the carrier gases nitrogen and argon, trimethylindium as an indium source and hydrogen sulphide as chalcogen source is provided in thefirst reaction zone 18 a. Due to the heating of the substrate, indium originating from themixture 77 a of trimethylindium and nitrogen and sulphur originating from themixture 79 b of hydrogen sulphide and argon carrier gas are converted into indium sulphide and deposited onto thesurface 2 of thesubstrate 1 as indium sulphide sublayer. - Further on, the
substrate 1 carrying theindium sulphide sub-layer 18 a is transported into asecond reaction zone 18 b. All transport of thesubstrates 1 is preferably done continuously. This means that thesubstrates 1 are continuously moved relatively to thereactor 70. - Via
gas inlets mixture 77 b of trimethylindium and the carrier gas nitrogen and amixture 79 b of hydrogen sulphide and argon gas as the carrier gas are fed into thesecond reaction zone 18 b. Therefore, by analogy with the indium sulphide sublayer 17 a in thefirst reaction zone 18 a, a furtherindium sulphide sublayer 17 b is deposited onto the previously deposited indium sulphide sublayer 17 a. Both indium sulphide sublayers 17 a, 17 b form together the final indium sulphide layer. Such a sequential deposition of indium sulphide sublayers makes it possible to produce indium sulphide layers of enhanced homogeneity. Furthermore, a thickness of the indium sulphide layer can be quite easily controlled. In principle, any number of indium sulphide sublayers can be deposited by elongating thereactor 70 and providing additional gas inlets. -
FIG. 3 schematically illustrates a further embodiment of the method according to the invention and simultaneously a first embodiment of an apparatus according to the invention. The apparatus schematically depicted inFIG. 3 differs from the one ofFIG. 2 in such that twopremixing devices mixture 83 of trimethylindium and nitrogen forming together an indium containing precursor gas and amixture 85 of 1,2-ethanedithiol and nitrogen are fed into each of thepremixing devices mixture 85 of 1,2-ethanedithiol and nitrogen represents a chalcogen containing precursor gas. The materials are premixed in thepremixing devices gaseous mixtures 86 are fed into thereactor 70 viainlet slots reactor 70 the gaseous mixtures are fed into the first 18 a andsecond reaction zone 18 b, respectively. In thereaction zones FIG. 2 , in thefirst reaction zone 18 a anindium sulphide sublayer 27 a is deposited onto thesurface 2 of thesubstrate 1, and in thesecond reaction zone 18 b a furtherindium sulphide sublayer 27 b is deposited onto the previously depositedindium sulphide sublayer 27 a. - Under atmospheric pressure trimethylindium is solid at room temperature. In order to provide the indium containing a precursor gas, a trimethylindium source is therefore preferably heated to a temperature between 25° C. and 75° C., so that the material partly sublimes. Further on, nitrogen is preferably provided as the carrier gas for trimethylindium vapor. Flowing above the trimethylindium source it carries away trimethylindium vapor and delivers it into the premixing devices. In this way growth rates of the indium sulphide layer can be improved.
- In the embodiment of
FIG. 3 and also in the embodiment ofFIG. 4 described below 1,2-ethanedithiol is premixed with trimethylindium. Obviously, these materials can also be used in the embodiments ofFIGS. 1 and 2 and vice versa. Apparently, also other material combinations are possible. In practice, the use of trimethylindium with a nitrogen carrier gas as indium containing a precursor gas in combination with hydrogen sulphide diluted into argon has proven itself. Therein, hydrogen sulphide diluted into argon represents the chalcogen containing a precursor gas. Such a gaseous mixture is preferably kept at a temperature of about 50° C. until it is fed into the reaction zone. -
FIG. 4 shows in a schematic illustration a further embodiment of the apparatus according to the invention and illustrates simultaneously a further embodiment of the method according to the invention. The apparatus differs from the one known fromFIG. 3 such that only onepremixing device 82 is provided instead of two. Furthermore, in contrast toFIG. 3 the gas inlets are realized by temperature controlled distribution heads 91 a, 91 b. Thegaseous mixture 86 is consequently fed from thepremixing device 82 into thereactor 70 and in the first andsecond reaction zones openings gaseous mixture 86 are provided via the distribution heads 91 a, 91 b. - By providing one
premixing device 82 for several, in this embodiment two, distribution heads 91 a, 91 b or gas inlets in general, complexity of the apparatus can be reduced. Apparently, the number of premixing devices and the number of gas inlets or distribution heads each premixing device supplies with the gaseous mixture can be adapted to individual needs. - Distribution heads, and particularly temperature controlled distribution heads, can obviously also be provided instead of gas inlets in the embodiments of
FIGS. 1 to 3 . Temperature controlled distribution heads are, however, particularly advantageous in the embodiments ofFIGS. 3 and 4 as they facilitate the temperature control of thegaseous mixture 86. - All the apparatus depicted in
FIGS. 1 to 4 can easily be integrated in inline production lines, so that a cost efficient deposition of indium chalcogenide layers at an industrial scale becomes possible. In particular, thin film solar cells can be advantageously produced using one of the methods and one of the apparatus according to the depicted embodiments. - In each of the embodiments of the apparatus depicted in
FIGS. 1 to 4 theheating device 72 can be omitted, if thesubstrates 1 are preheated outside thereactor 70 such that on reaching thereaction zone 8; 18 a, 18 b their temperature is still high enough to enable the conversion of indium originating from the indium source and the chalcogen originating from the source of a chalcogen to an indium chalcogenide. -
FIG. 5 schematically illustrates asolar cell 49 according to the invention. It contains aglass substrate 50 covered by amolybdenum layer 52. ACIGS layer 54 serving as absorber layer is formed on the molybdenum layer. Upon thisCIGS layer 54 anindium sulphide layer 57 formed by chemical vapor deposition at approximately atmospheric ambient pressure is provided as a buffer layer. Azinc oxide layer 59 is provided on theindium sulphide layer 57 as a transparent conducting layer. - The
solar cell 49 can be manufactured using one of the methods and apparatus illustrated inFIGS. 1 to 4 . Thesubstrate 1 inFIGS. 1 to 4 would then be formed by theglass substrate 50, themolybdenum layer 52 and theCIGS layer 54. Thesurface 2 onto which the indium sulphide is deposited, would then be an upper surface of theCIGS layer 54. This makes clear again, that for the purpose of the present invention the term substrate refers to anything an indium chalcogenide layer can be deposited on. In particular it can mean a glass substrate carrying a metal back contact layer and an absorber layer of a thin film solar cell.
Claims (27)
1. A method for depositing a layer of an indium chalcogenide onto a substrate, which comprises the steps of:
providing an indium source in a reaction zone;
providing a gaseous source of a chalcogen in the reaction zone; and
heating the substrate and thereby in the reaction zone converting at a pressure of approximately atmospheric ambient pressure indium originating from the indium source and the chalcogen originating from the gaseous source of the chalcogen to an indium chalcogenide being deposited onto a surface of the substrate.
2. The method according to claim 1 , which further comprises providing the indium source in the reaction zone by depositing an indium containing compound onto the surface of the substrate and disposing the substrate at least partly in the reaction zone.
3. The method according to claim 1 , which further comprises providing a gaseous mixture containing a carrier gas, the indium source and the chalcogen source in the reaction zone.
4. The method according to claim 3 , which further comprises:
premixing an indium containing a precursor gas with the chalcogen containing a precursor gas and a carrier gas forming a resulting mixture; and
delivering the resulting mixture as a gaseous mixture into the reaction zone, while a gaseous component contained in at least one of the indium and the chalcogen containing the precursor gas is used as a carrier gas.
5. The method according to claim 4 , wherein at least one of the precursor gases contains a stabilizing adduct group.
6. The method according to claim 3 , which further comprises forming the gaseous mixture by mixing an indium containing the precursor gas with a chalcogen containing the precursor gas and a carrier gas close to or in the reaction zone, while a gaseous component contained in at least one of the indium and the chalcogen containing the precursor gas is used as the carrier gas.
7. The method according to claim 3 , which further comprises providing at least one precursor gas via at least one distribution head.
8. The method according to claim 1 , which further comprises depositing the indium chalcogenide as a buffer layer of a solar cell.
9. The method according to claim 1 , which further comprises using at least one at atmospheric pressure volatile indium compound as the indium source.
10. The method according to claim 9 , which further comprises using at least one indium alkyl compound as the indium source.
11. The method according to claim 10 , which further comprises using an indium compound as the indium source which contains at least one alkyl group and at least one further functional group selected from the group consisting of a hydrogen group, a halide group and an acetate group.
12. The method according to claim 1 , which further comprises using at atmospheric ambient pressure volatile a chalcogen compound as the gaseous source of the chalcogen.
13. The method according to claim 1 , which further comprises depositing a metal layer and subsequently an absorber layer onto the substrate before the indium chalcogenide is deposited onto the surface of the substrate.
14. The method according to claim 2 , which further comprises providing the indium containing compound as an indium oxide.
15. The method according to claim 5 wherein the stabilizing adduct group is based on an element selected from the group consisting of sulphur, oxygen and electron donating nitrogen.
16. The method according to claim 7 , wherein the at least one distribution head is a temperature controlled distribution head.
17. The method according to claim 9 , wherein the volatile indium compound is an indium compound having the formula InCxHy, where x ranges from 3 to 20 and y ranges from 9 to 39.
18. The method according to claim 9 , which further comprises using trimethylindium as the indium source.
19. The method according to claim 12 , which further comprises selecting the chalcogen compound from the group consisting of a sulphur compound, a hydrogen sulphide and an organosulphur compound.
20. The method according to claim 13 , which further comprises:
providing a molybdenum layer as the metal layer; and
providing an absorber layer containing a compound represented by the formula Cu(In,Ga)(S,Se)2 as the absorber layer.
21. The method according to claim 9 , which further comprises depositing the indium chalcogenide, being an indium sulphide layer, as a buffer layer of a solar cell.
22. A solar cell, comprising:
an absorber layer formed by a compound semiconductor and a buffer layer, said buffer layer being formed by chemical vapor deposition of an indium chalcogenide at approximately atmospheric ambient pressure and being an indium chalcogenide layer.
23. The solar cell according to claim 22 , wherein said indium chalcogenide layer is formed by:
providing an indium source in a reaction zone;
providing a gaseous source of a chalcogen in said reaction zone; and
heating a substrate and thereby in the reaction zone converting at a pressure of approximately atmospheric ambient pressure indium originating from the indium source and the chalcogen originating from the gaseous source of the chalcogen to an indium chalcogenide being deposited onto a surface of the substrate.
24. An apparatus for depositing a layer of an indium chalcogenide onto a substrate, comprising:
a reactor, into which substrates can be introduced;
a gas inlet slot for feeding gases into said reactor;
a transport device for moving the substrates through said reactor; and
at least one premixing device for premixing an indium containing a precursor gas with a chalcogen containing a precursor gas and that a gaseous mixture can be fed from said at least one premixing device into said reactor via said gas inlet slot.
25. The apparatus according to claim 24 , wherein said gas inlet slot is one of several gas inlet slots disposed at a distance from each other in a transport direction of said transport device.
26. The apparatus according to claim 24 ,
wherein said reactor has at least one opening formed therein for introducing the substrates into or discharging the substrates from said reactor; and
further comprising a gas lock disposed at said at least one opening.
27. The apparatus according to claim 24 , further comprising a heating device for heating the substrates.
Applications Claiming Priority (2)
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EP09009994.6 | 2009-07-24 | ||
EP09009994A EP2278625A1 (en) | 2009-07-24 | 2009-07-24 | Method and apparatus for deposition of a layer of an Indium Chalcogenide onto a substrate |
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US20110017283A1 true US20110017283A1 (en) | 2011-01-27 |
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US12/843,431 Abandoned US20110017283A1 (en) | 2009-07-24 | 2010-07-26 | Method and apparatus for deposition of a layer of an indium chalcogenide onto a substrate |
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US20110104876A1 (en) * | 2008-04-01 | 2011-05-05 | Helmholtz-Zentrum Berlin Fuer Materialien Und Energie Gmbh | Atmospheric pressure chemical vapor deposition method for producing a n-semiconductive metal sulfide thin layer |
US20120094428A1 (en) * | 2010-10-15 | 2012-04-19 | Electronics And Telecommunications Research Institute | Manufacturing method of compound semiconductor solar cell |
US20140144772A1 (en) * | 2012-11-29 | 2014-05-29 | Corning Incorporated | High rate deposition systems and processes for forming hermetic barrier layers |
US20160233360A1 (en) * | 2012-06-20 | 2016-08-11 | Saint-Gobain Glass France | Layer system for thin-film solar cells |
US9461186B2 (en) | 2010-07-15 | 2016-10-04 | First Solar, Inc. | Back contact for a photovoltaic module |
CN113445025A (en) * | 2021-06-03 | 2021-09-28 | 东北林业大学 | Preparation of wafer-level two-dimensional In by chemical vapor deposition2Se3Method for making thin film |
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US20110104876A1 (en) * | 2008-04-01 | 2011-05-05 | Helmholtz-Zentrum Berlin Fuer Materialien Und Energie Gmbh | Atmospheric pressure chemical vapor deposition method for producing a n-semiconductive metal sulfide thin layer |
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US20100203668A1 (en) | 2007-09-11 | 2010-08-12 | Centrotherm Photovoltaics Ag | Method and apparatus for thermally converting metallic precursor layers into semiconducting layers, and also solar module |
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US4611091A (en) * | 1984-12-06 | 1986-09-09 | Atlantic Richfield Company | CuInSe2 thin film solar cell with thin CdS and transparent window layer |
US20110104876A1 (en) * | 2008-04-01 | 2011-05-05 | Helmholtz-Zentrum Berlin Fuer Materialien Und Energie Gmbh | Atmospheric pressure chemical vapor deposition method for producing a n-semiconductive metal sulfide thin layer |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
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US20110104876A1 (en) * | 2008-04-01 | 2011-05-05 | Helmholtz-Zentrum Berlin Fuer Materialien Und Energie Gmbh | Atmospheric pressure chemical vapor deposition method for producing a n-semiconductive metal sulfide thin layer |
US8609516B2 (en) * | 2008-04-01 | 2013-12-17 | Helmholtz-Zentrum Berlin Fuer Materialien Und Energie Gmbh | Atmospheric pressure chemical vapor deposition method for producing an-N-semiconductive metal sulfide thin layer |
US9461186B2 (en) | 2010-07-15 | 2016-10-04 | First Solar, Inc. | Back contact for a photovoltaic module |
US20120094428A1 (en) * | 2010-10-15 | 2012-04-19 | Electronics And Telecommunications Research Institute | Manufacturing method of compound semiconductor solar cell |
US8258003B2 (en) * | 2010-10-15 | 2012-09-04 | Electronics And Telecommunications Research Institute | Manufacturing method of compound semiconductor solar cell |
US20160233360A1 (en) * | 2012-06-20 | 2016-08-11 | Saint-Gobain Glass France | Layer system for thin-film solar cells |
US10134931B2 (en) * | 2012-06-20 | 2018-11-20 | Bengbu Design & Research Institute For Glass Industry | Layer system for thin-film solar cells |
US20140144772A1 (en) * | 2012-11-29 | 2014-05-29 | Corning Incorporated | High rate deposition systems and processes for forming hermetic barrier layers |
US10017849B2 (en) * | 2012-11-29 | 2018-07-10 | Corning Incorporated | High rate deposition systems and processes for forming hermetic barrier layers |
CN113445025A (en) * | 2021-06-03 | 2021-09-28 | 东北林业大学 | Preparation of wafer-level two-dimensional In by chemical vapor deposition2Se3Method for making thin film |
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